JPH06263776A - Phosphine compound and transition metal-phosphine complex containing the compound as ligand - Google Patents
Phosphine compound and transition metal-phosphine complex containing the compound as ligandInfo
- Publication number
- JPH06263776A JPH06263776A JP5253893A JP5253893A JPH06263776A JP H06263776 A JPH06263776 A JP H06263776A JP 5253893 A JP5253893 A JP 5253893A JP 5253893 A JP5253893 A JP 5253893A JP H06263776 A JPH06263776 A JP H06263776A
- Authority
- JP
- Japan
- Prior art keywords
- phosphine
- compound
- transition metal
- mmol
- rhodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 48
- -1 Phosphine compound Chemical class 0.000 title claims abstract description 34
- 150000001875 compounds Chemical class 0.000 title claims abstract description 23
- 239000003446 ligand Substances 0.000 title claims description 17
- 230000007704 transition Effects 0.000 title claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 3
- 239000010948 rhodium Substances 0.000 claims description 41
- 229910052703 rhodium Inorganic materials 0.000 claims description 16
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 10
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims 4
- VYXHVRARDIDEHS-QGTKBVGQSA-N (1z,5z)-cycloocta-1,5-diene Chemical group C\1C\C=C/CC\C=C/1 VYXHVRARDIDEHS-QGTKBVGQSA-N 0.000 claims 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 125000002872 norbornadienyl group Chemical group C12=C(C=C(CC1)C2)* 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 30
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 239000003054 catalyst Substances 0.000 abstract description 17
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 39
- 238000012937 correction Methods 0.000 description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- 238000003786 synthesis reaction Methods 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 22
- 239000000203 mixture Substances 0.000 description 22
- 239000002904 solvent Substances 0.000 description 22
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 230000003287 optical effect Effects 0.000 description 17
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000007037 hydroformylation reaction Methods 0.000 description 11
- 239000012044 organic layer Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 9
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 238000010898 silica gel chromatography Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000011914 asymmetric synthesis Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 6
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 5
- FXPPNKAYSGWCQG-UHFFFAOYSA-N 2-acetoxypropanal Chemical compound O=CC(C)OC(C)=O FXPPNKAYSGWCQG-UHFFFAOYSA-N 0.000 description 5
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical class C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- YPGCWEMNNLXISK-UHFFFAOYSA-N hydratropic acid Chemical compound OC(=O)C(C)C1=CC=CC=C1 YPGCWEMNNLXISK-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 125000005951 trifluoromethanesulfonyloxy group Chemical group 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- WTLNOANVTIKPEE-UHFFFAOYSA-N 2-acetyloxypropanoic acid Chemical compound OC(=O)C(C)OC(C)=O WTLNOANVTIKPEE-UHFFFAOYSA-N 0.000 description 2
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 2
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 description 2
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 238000006809 Jones oxidation reaction Methods 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- VFYNVDRWOAJSKI-UHFFFAOYSA-N chloro(diphenoxy)phosphane Chemical compound C=1C=CC=CC=1OP(Cl)OC1=CC=CC=C1 VFYNVDRWOAJSKI-UHFFFAOYSA-N 0.000 description 2
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- 239000005052 trichlorosilane Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RJUFATJOENABQE-UHFFFAOYSA-N (2,2,2-trichloro-1-diphenoxyphosphorylethyl) acetate Chemical compound C=1C=CC=CC=1OP(=O)(C(C(Cl)(Cl)Cl)OC(=O)C)OC1=CC=CC=C1 RJUFATJOENABQE-UHFFFAOYSA-N 0.000 description 1
- WTLNOANVTIKPEE-VKHMYHEASA-N (2s)-2-acetyloxypropanoic acid Chemical compound OC(=O)[C@H](C)OC(C)=O WTLNOANVTIKPEE-VKHMYHEASA-N 0.000 description 1
- YPGCWEMNNLXISK-ZETCQYMHSA-N (S)-hydratropic acid Chemical compound OC(=O)[C@@H](C)C1=CC=CC=C1 YPGCWEMNNLXISK-ZETCQYMHSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- LWZAKMZAVUALLD-UHFFFAOYSA-N 1-(2-diphenylphosphanylnaphthalen-1-yl)naphthalen-2-ol Chemical group OC1=CC=C2C=CC=CC2=C1C(C1=CC=CC=C1C=C1)=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 LWZAKMZAVUALLD-UHFFFAOYSA-N 0.000 description 1
- LXXVKDWVNIWBIF-UHFFFAOYSA-N 1-(2-phosphanylnaphthalen-1-yl)naphthalen-2-ol Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(P)C=CC2=C1 LXXVKDWVNIWBIF-UHFFFAOYSA-N 0.000 description 1
- XWILPQCBLAXRHF-UHFFFAOYSA-N 2-acetamido-3-(4-acetyloxy-3-methoxyphenyl)prop-2-enoic acid Chemical compound COC1=CC(C=C(NC(C)=O)C(O)=O)=CC=C1OC(C)=O XWILPQCBLAXRHF-UHFFFAOYSA-N 0.000 description 1
- IQVAERDLDAZARL-UHFFFAOYSA-N 2-phenylpropanal Chemical compound O=CC(C)C1=CC=CC=C1 IQVAERDLDAZARL-UHFFFAOYSA-N 0.000 description 1
- PRSPLAWXBFRHKV-UHFFFAOYSA-N 3-oxopropyl acetate Chemical compound CC(=O)OCCC=O PRSPLAWXBFRHKV-UHFFFAOYSA-N 0.000 description 1
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 description 1
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical class NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 1
- 241001530392 Aphos Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- SIAOTHPVLMQEEA-UHFFFAOYSA-N FC(F)(F)S(=O)(=O)Oc1ccc2ccccc2c1-c1c(ccc2ccccc12)[PH2]=O Chemical group FC(F)(F)S(=O)(=O)Oc1ccc2ccccc2c1-c1c(ccc2ccccc12)[PH2]=O SIAOTHPVLMQEEA-UHFFFAOYSA-N 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- OYJLCOSEYYZULE-UHFFFAOYSA-N [1-[2-(trifluoromethylsulfonyloxy)naphthalen-1-yl]naphthalen-2-yl] trifluoromethanesulfonate Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3OS(=O)(=O)C(F)(F)F)=C(OS(=O)(=O)C(F)(F)F)C=CC2=C1 OYJLCOSEYYZULE-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229930003633 citronellal Natural products 0.000 description 1
- 235000000983 citronellal Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0073—Rhodium compounds
- C07F15/008—Rhodium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は新規なホスフィン化合物
およびこれを配位子とする種々の不斉合成反応の触媒と
して有用な遷移金属錯体に関する。FIELD OF THE INVENTION The present invention relates to a novel phosphine compound and a transition metal complex having the ligand as a ligand and useful as a catalyst for various asymmetric synthesis reactions.
【0002】[0002]
【従来の技術】従来より、多くの遷移金属錯体が有機合
成反応の触媒として使用されており、特に、貴金属錯体
は高価であるが、安定で取扱いが容易であるため、これ
を触媒として使用する多くの合成研究がなされ、これま
での手段では不可能とされていた有機合成反応を可能に
した数多くの報告が次々となされている。2. Description of the Related Art Conventionally, many transition metal complexes have been used as catalysts for organic synthetic reactions. Particularly, noble metal complexes are expensive, but they are stable and easy to handle. Many synthetic studies have been carried out, and many reports have been made one after another that have enabled organic synthetic reactions that were impossible by conventional means.
【0003】その中でも、ロジウム、パラジウム、ルテ
ニウム、ニッケル等の遷移金属に光学活性な第3級ホス
フィンを配位させた錯体には、不斉合成反応の触媒とし
て優れた性能を有するものが多く、この触媒の性能を高
めるために、これまでに特殊な構造のホスフィン化合物
が数多く開発されてきた(日本化学会編、化学総説32
「有機金属の化学」、237−238頁、昭和57
年)。Among them, many complexes having an optically active tertiary phosphine coordinated with a transition metal such as rhodium, palladium, ruthenium and nickel have excellent properties as catalysts for asymmetric synthesis reaction, To improve the performance of this catalyst, many phosphine compounds with a special structure have been developed so far (edited by The Chemical Society of Japan, Review of Chemistry 32).
"Organic Metal Chemistry", pp. 237-238, Showa 57
Year).
【0004】例えば、特開昭55−61937号公報に
は、不斉水素化反応触媒として、キラルなホスフィンを
ロジウムに配位させたロジウム−ホスフィン錯体が記載
されており、また、特開昭58−4748号公報には不
斉異性化触媒としてロジウム−光学活性ホスフィン錯体
を用いてアリルアミン誘導体を不斉異性化した後、数工
程を経て光学活性シトロネラールを得る方法が記載され
ている。For example, JP-A-55-61937 discloses a rhodium-phosphine complex in which a chiral phosphine is coordinated with rhodium as an asymmetric hydrogenation reaction catalyst, and JP-A-58-58. No. 4748 discloses a method of obtaining an optically active citronellal through several steps after asymmetrically isomerizing an allylamine derivative using a rhodium-optically active phosphine complex as an asymmetric isomerization catalyst.
【0005】特開昭59−20294号公報にはロジウ
ム−BINAP錯体(BINAPは2,2′−ビス(ジ
フェニルホスフィノ)−1,1′−ビナフチルを表す)
を用いた3−メトキシ−4−アセトキシ−α−アセトア
ミドケイ皮酸の不斉水素添化反応が記載されている。ま
た、このBINAPを配位させたルテニウム錯体(特開
昭61−63690号公報)も知られており、これらの
錯体は不斉異性化反応、不斉水素化反応において優れた
性能を有している。JP-A-59-20294 discloses a rhodium-BINAP complex (BINAP stands for 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl).
Describes an asymmetric hydrogenation reaction of 3-methoxy-4-acetoxy-α-acetamidocinnamic acid using. Further, ruthenium complexes in which this BINAP is coordinated (Japanese Patent Laid-Open No. 61-63690) are also known, and these complexes have excellent performance in asymmetric isomerization reaction and asymmetric hydrogenation reaction. There is.
【0006】更にまた、遷移金属−光学活性ホスフィン
錯体を用いる不斉ヒドロホルミル化反応が知られてい
る。すなわち、ジャーナル・オブ・オーガニック・ケミ
ストリー(J.Org.Chem.)、第46巻、44
22〜4427頁、1981年には、光学活性な2,3
−O−イソプロピリデン−2,3−ジヒドロキシ−1,
4−ビス(ジフェニルホスフィノ)ブタン(以下、DI
OPという)を配位子とするロジウム錯体を用いる不斉
ヒドロホルミル化反応が;ブルテン・オブ・ザ・ケミカ
ル・ソサイアティ・オブ・ジャパン(Bull.Che
m.Soc.Japan)、第52巻、2605〜26
08頁、1979年には、光学活性な二座ホスフィン
(DIOP等)を配位子とするロジウム錯体を用いるオ
レフィン類の不斉ヒドロホルミル化反応が;また、テト
ラヘドロン・アシンメトリー(Tetrahedron
Asymmetry)、第10巻、693〜696
頁、1990年には、光学活性な二座ホスフィン、例え
ばDIOPを配位子とするロジウム錯体を用いるα−ア
セトアミドアクリル酸メチルの不斉ヒドロホルミル化反
応が記載されている。Furthermore, an asymmetric hydroformylation reaction using a transition metal-optically active phosphine complex is known. That is, Journal of Organic Chemistry (J. Org. Chem.), Vol. 46, 44.
22-4427, in 1981, optically active 2,3
-O-isopropylidene-2,3-dihydroxy-1,
4-bis (diphenylphosphino) butane (hereinafter, DI
Asymmetric hydroformylation reaction using a rhodium complex having OP as a ligand; Bulletin of the Chemical Society of Japan (Bull. Che)
m. Soc. Japan), Volume 52, 2605-26
08, 1979, the asymmetric hydroformylation reaction of olefins using a rhodium complex having an optically active bidentate phosphine (DIOP etc.) as a ligand; also, tetrahedron asymmetry (Tetrahedron
Asymmetry), Volume 10, 693-696
Page, 1990 describes an asymmetric hydroformylation reaction of methyl α-acetamidomethyl acrylate using a rhodium complex having an optically active bidentate phosphine, for example, DIOP as a ligand.
【0007】光学活性な第3級ホルファイトを配位子と
する錯体としては、例えばテトラヘドロン・アシンメト
リー(Tetrahedron Asymmetr
y)、第3巻、583〜586頁、1992年に、光学
活性なBINAP構造を有するビス(トリアリールホス
ファイト)が記載されており、このものを配位子とする
ロジウム錯体を用いた酢酸ビニルの不斉ヒドロホルミル
化反応が記載されている。Examples of the complex having an optically active tertiary phosphite as a ligand include tetrahedron asymmetry (Tetrahedron Asymmetr).
y), Vol. 3, pp. 583-586, 1992 describes a bis (triarylphosphite) having an optically active BINAP structure. Acetic acid using a rhodium complex having this as a ligand is described. The asymmetric hydroformylation reaction of vinyl has been described.
【0008】また、ロジウム以外の金属としては、オル
ガノメタリクス(organometallics)、
第10巻、1183〜1189頁、1991年に、光学
活性1−(t−ブトキシカルボニル)−4−(ジベンゾ
ホスホニル)−2−[(ジベンゾホスホリル)メチル]
ピロリジンを配位子とした白金錯体が優れた性能を有し
ていることが知られている。Metals other than rhodium include organometallics,
Vol. 10, 1183-1189, 1991, optically active 1- (t-butoxycarbonyl) -4- (dibenzophosphonyl) -2-[(dibenzophosphoryl) methyl].
It is known that a platinum complex having pyrrolidine as a ligand has excellent performance.
【0009】[0009]
【発明が解決しようとする課題】上述のように、不斉合
成反応の触媒としてより高い性能を有する触媒を提供す
るために、これまでに特殊なホスフィン化合物が多数開
発されているが、これらも対象とする基質や反応によっ
ては選択性、転化率、触媒活性、光学純度等の面で充分
に満足できない場合があった。従って、本発明は従来の
触媒に比べて高い触媒能を有する錯体を与える新しいホ
スフィン化合物を提供することを目的とするものであ
る。As described above, many special phosphine compounds have been developed so far in order to provide a catalyst having higher performance as a catalyst for an asymmetric synthesis reaction. Depending on the target substrate or reaction, there were cases where the selectivity, conversion rate, catalytic activity, optical purity, etc. could not be fully satisfied. Therefore, it is an object of the present invention to provide a new phosphine compound which gives a complex having higher catalytic ability than conventional catalysts.
【0010】[0010]
【課題を解決するための手段】斯かる実情において、本
発明者は上記課題を解決せんと鋭意研究を行った結果、
光学活性なビナフトールを骨格とするホスフィン化合物
を配位子とする遷移金属錯体が、従来公知の光学活性ホ
スフィン遷移金属錯体に比べ、不斉合成における光学純
度および選択率において著しく優っていることを見出
し、本発明を完成した。Under the circumstances, the present inventor has conducted earnest research to solve the above problems, and as a result,
It was found that the transition metal complex having an optically active phosphine compound having a skeleton of binaphthol as a ligand is remarkably superior to the conventionally known optically active phosphine transition metal complex in optical purity and selectivity in asymmetric synthesis. The present invention has been completed.
【0011】従って、本発明は、次の一般式(1)Therefore, the present invention provides the following general formula (1):
【0012】[0012]
【化3】 [Chemical 3]
【0013】(式中、R1およびR2は同一または異なっ
て、ハロゲン原子または低級アルキル基で置換されてい
てもよいフェニル基を示すか、R1とR2が共同して2価
の炭化水素基を示し、R3およびR4は同一または異なっ
て、低級アルキル基またはハロゲン原子、低級アルキル
基もしくは低級アルコキシ基で置換されていてもよいフ
ェニル基を示すか、R3とR4が共同して2価の炭化水素
基を示す)で表わされるホスフィン化合物を提供するも
のである。(In the formula, R 1 and R 2 are the same or different and each represents a phenyl group which may be substituted with a halogen atom or a lower alkyl group, or R 1 and R 2 together form a divalent carbon atom. A hydrogen group, R 3 and R 4 are the same or different and each represents a lower alkyl group or a phenyl group which may be substituted with a halogen atom, a lower alkyl group or a lower alkoxy group, or R 3 and R 4 are jointly present. To represent a divalent hydrocarbon group).
【0014】本発明は、更に、このホスフィン化合物を
配位子とする遷移金属−ホスフィン錯体を提供するもの
である。遷移金属としてはロジウム、ルテニウム、パラ
ジウム、イリジウム、白金、コバルト、ニッケル、チタ
ン等を挙げることができ、遷移金属がロジウムの場合の
ロジウム−ホスフィン錯体は次の一般式(2−a)また
は(2−b)で表わされる。The present invention further provides a transition metal-phosphine complex having the phosphine compound as a ligand. Examples of the transition metal include rhodium, ruthenium, palladium, iridium, platinum, cobalt, nickel and titanium. When the transition metal is rhodium, the rhodium-phosphine complex has the following general formula (2-a) or (2 -B).
【0015】[0015]
【化4】 [Chemical 4]
【0016】(式中、Lはホスフィン化合物を示し、Y
は一酸化炭素、これより配位力の弱い単座もしくは二座
の中性配位子、オレフィンまたはジエンを示し、Xは水
素原子、1価の陰イオンまたはトリフェニルホスフィン
を示すか、あるいはXとYが一緒になってβ−ジケトナ
ートを示す)(Wherein L represents a phosphine compound, and Y
Represents carbon monoxide, a monodentate or bidentate neutral ligand having a weaker coordination power, an olefin or a diene, and X represents a hydrogen atom, a monovalent anion or triphenylphosphine, or Y together represents β-diketonate)
【0017】本発明のホスフィン化合物(1)は、例え
ば次の反応式によって示される方法により製造される。The phosphine compound (1) of the present invention is produced, for example, by the method represented by the following reaction formula.
【0018】[0018]
【化5】 [Chemical 5]
【0019】(式中、Tfはトリフルオロメタンスルホ
ニル基を示し、R1、R2、R3およびR 4 は前記と同じ
ものを示す) すなわち、テトラヘドロン・レターズ(Tetrahe
dron Letters)、第31巻、6321〜6
324頁、1990年に記載の方法に準じて、1,1−
ビ−2−ナフトール(3)にトリフルオロメタンスルホ
ン酸無水物(4)を反応せしめて2,2′−ビス(トリ
フルオロメタンスルホニルオキシ)−1,1′−ビナフ
チル(5)となし、これにパラジウム触媒の存在下、ホ
スフィンオキシド(6)を反応せしめて2−オキソホス
フィノ−2′−トリフルオロメタンスルホニルオキシ−
1,1′−ビナフチル(7)となし、次いでこれをトリ
エチルアミンの存在下還元した後、加水分解して2−ホ
スフィノ−2′−ヒドロキシ−1,1′−ビナフチル
(8)となし、更にこれにクロロホスフィン(9)をト
リエチルアミンの存在下反応せしめれば、本発明のホス
フィン化合物(1)が製造される。(Where TfIs trifluoromethanesulfo
Represents a nyl group, R1, R2, R3And R FourIs the same as above
That is, Tetrahedron Letters (Tetrahhe)
dron Letters), Volume 31, 6321-6
324, 1,1 according to the method described in 1990
Bi-2-naphthol (3) with trifluoromethanesulfone
The acid anhydride (4) was reacted to react with 2,2'-bis (tri
Fluoromethanesulfonyloxy) -1,1′-binaphth
Chill (5), in the presence of a palladium catalyst,
React with sphine oxide (6) to give 2-oxophos
Fino-2'-trifluoromethanesulfonyloxy-
No 1,1'-binaphthyl (7), then tri-
After reduction in the presence of ethylamine, hydrolysis is performed to
Sufino-2'-hydroxy-1,1'-binaphthyl
(8) and add chlorophosphine (9) to it.
If the reaction is carried out in the presence of triethylamine, the phosphine of the present invention can be obtained.
The fin compound (1) is produced.
【0020】本発明で原料として使用される光学活性な
1,1′−ビ−2−ナフトールは、J.Org.Che
m.1988,53,3607および特開昭64−13
063号公報に開示された方法により、天然型または非
天然型酒石酸を原料として合成された光学活性なO,
O′−ジメチル−N,N′−テトラメチル酒石酸アミド
とラセミビナフトールの一方の光学活性体とのみ包接錯
体を形成させ、次いでその錯体を分解することにより、
容易に高光学純度かつ高収率で合成することができる。The optically active 1,1'-bi-2-naphthol used as a raw material in the present invention is described in J. Org. Che
m. 1988 , 53, 3607 and JP-A-64-13.
The optically active O, which is synthesized from the natural or non-natural tartaric acid as a raw material by the method disclosed in Japanese Patent Application No. 063
By forming an inclusion complex only with O'-dimethyl-N, N'-tetramethyltartaric acid amide and one optically active form of racemic binaphthol, and then decomposing the complex,
It can be easily synthesized with high optical purity and high yield.
【0021】また、本発明の遷移金属−ホスフィン錯体
(2)は、公知の方法に準じて製造することができる。
例えば、J.Am.Chem.Soc.,93,308
9(1971)に記載の方法に従って、[Rh(COD)
(Cl)]2(COD:1,5−シクロオクタジエン)、
あるいはCODおよびAgClO4から製造した〔Rh
(COD)2〕ClO4と本発明のホスフィン化合物(1)
(L)を反応せしめれば〔Rh(L)(COD)〕Cl
O4が得られる。The transition metal-phosphine complex (2) of the present invention can be produced according to a known method.
For example, J. Am. Chem. Soc. , 93 , 308
9 (1971) according to the method described in [Rh (COD)
(Cl)] 2 (COD: 1,5-cyclooctadiene),
Alternatively, it was prepared from COD and AgClO 4 [Rh
(COD) 2 ] ClO 4 and the phosphine compound (1) of the present invention
If (L) is reacted, [Rh (L) (COD)] Cl
O 4 is obtained.
【0022】更に、Inorg.Synth.,8,2
14〜217(1966)に記載の方法に従って、市販
の[Rh(CO)2Cl]2に本発明のホスフィン化合物
(1)を塩化メチレン中、室温下に反応せしめれば〔R
h(L)(CO)Cl〕が得られる。Further, Inorg. Synth. , 8 , 2
14-217 (1966), the commercially available [Rh (CO) 2 Cl] 2 is reacted with the phosphine compound (1) of the present invention in methylene chloride at room temperature.
h (L) (CO) Cl] is obtained.
【0023】なお、本発明のホスフィン化合物(1)の
ビナフチル骨格には光学活性体及びラセミ体が存在する
が、本発明はこれらの化合物のいずれも含むものであ
る。The binaphthyl skeleton of the phosphine compound (1) of the present invention has an optically active substance and a racemate, but the present invention includes any of these compounds.
【0024】本発明において、ロジウム−ホスフィン錯
体としては次のものが例示される。なお、ここにおい
て、LおよびCODは前記と同じものを示し、NBDは
ノルボルナジエンを、Phはフェニル基を、acacは
アセチルアセトナートを示す。[M(L)(C2H4)Cl]、[M
(L)(C2H4)Br]、[M(L)(C2H4)F]、[M(L)(C2H4)I]、
[M(L)(C2H4)CN]、[M(L)(CO)Cl]、[M(L)(CO)Br]、
[M(L)(CO)F]、[M(L)(CO)I]、[M(L)(CO)CN]、[M
(L)(COD)]Cl、[M(L)(COD)]Br、[M(L)(COD)]F、[M
(L)(COD)]I、[M(L)(COD)]ClO4、[M(L)(COD)]BF4、
[M(L)(COD)]PF6、[M(L)(COD)]CN、[M(L)(COD)]OC
OCH3、[M(L)(NBD)]Cl、[M(L)(NBD)]Br、[M(L)(NB
D)]F、[M(L)(NBD)]I、[M(L)(NBD)]ClO4、[M(L)(N
BD)]BF4、[M(L)(NBD)]PF6、[M(L)(NBD)]CN、[M
(L)(NBD)]OCOCH3、[M(L)(CO)2]H、[M(L)(CO)2(PP
h3)2]、[M(L)(CO)3(PPh3)]、[M(L)(ピリジン)Cl]、
[M(L)(ピリジン)Br]、[M(L)(acac)]In the present invention, the following are exemplified as the rhodium-phosphine complex. Here, L and COD are the same as described above, NBD is norbornadiene, Ph is a phenyl group, and acac is acetylacetonate. [M (L) (C 2 H 4 ) Cl], [M
(L) (C 2 H 4 ) Br], [M (L) (C 2 H 4 ) F], [M (L) (C 2 H 4 ) I],
[M (L) (C 2 H 4 ) CN], [M (L) (CO) Cl], [M (L) (CO) Br],
[M (L) (CO) F], [M (L) (CO) I], [M (L) (CO) CN], [M
(L) (COD)] Cl, [M (L) (COD)] Br, [M (L) (COD)] F, [M
(L) (COD)] I, [M (L) (COD)] ClO 4 , [M (L) (COD)] BF 4 ,
[M (L) (COD)] PF 6 , [M (L) (COD)] CN, [M (L) (COD)] OC
OCH 3 , [M (L) (NBD)] Cl, [M (L) (NBD)] Br, [M (L) (NB
D)] F, [M (L) (NBD)] I, [M (L) (NBD)] ClO 4 , [M (L) (N
BD)] BF 4 , [M (L) (NBD)] PF 6 , [M (L) (NBD)] CN, [M
(L) (NBD)] OCOCH 3 , [M (L) (CO) 2 ] H, [M (L) (CO) 2 (PP
h 3) 2], [M (L) (CO) 3 (PPh 3)], [M (L) ( pyridine) Cl],
[M (L) (pyridine) Br], [M (L) (acac)]
【0025】本発明の遷移金属−ホスフィン錯体は、例
えばオレフィン類の不斉ヒドロホルミル化反応の触媒と
して用いると、従来では達成することのできなかった高
い光学純度で目的の生成物を得ることができる。そし
て、本発明のホスフィン化合物の旋光度(+)体のも
の、または旋光度が(−)体のものの何れか一方を選択
し、これを配位子とした遷移金属−ホスフィン錯体を触
媒として用いることにより、不斉合成において所望する
絶対配置の目的物を高い光学純度で得ることができる。
また、例えば遷移金属としてロジウムを使用した場合に
は、ロジウム−ホスフィン錯体に、過剰のホスフィン化
合物を加えたもの、あるいは市販の[Rh(CO)2(a
cac)]等の触媒前駆体に、ロジウムに対して2〜4
当量の本発明ホスフィン化合物(1)を混合したものを
触媒として用いても同様の結果が得られる。また、触媒
前駆体としてRh6(CO)16、Rh4(CO)12等のロジウ
ムカルボニルクラスターを用いても有用な触媒となる。
また予めRhn(CO)nとハロゲンを反応させた後、ホス
フィン化合物を組合せて用いてもよい。なお、遷移金属
−ホスフィン錯体は、通常錯体中にRh原子が1個の単
核錯体であるが、Rh原子が2個以上の複核錯体の場合
もある。When the transition metal-phosphine complex of the present invention is used, for example, as a catalyst for an asymmetric hydroformylation reaction of olefins, a desired product can be obtained with a high optical purity which has hitherto been unattainable. . Then, the phosphine compound of the present invention is selected from either one having the optical rotatory power (+) or one having the optical rotatory power (-), and the transition metal-phosphine complex having this as a ligand is used as a catalyst. As a result, the desired product having the desired absolute configuration in the asymmetric synthesis can be obtained with high optical purity.
Further, for example, when rhodium is used as a transition metal, a rhodium-phosphine complex to which an excess of a phosphine compound is added, or a commercially available [Rh (CO) 2 (a
cac)] to catalyst precursors such as 2-4 for rhodium
Similar results are obtained even when a mixture of equivalent amounts of the phosphine compound (1) of the present invention is used as a catalyst. Further, a rhodium carbonyl cluster such as Rh 6 (CO) 16 or Rh 4 (CO) 12 may be used as a catalyst precursor, which is also a useful catalyst.
Alternatively, Rh n (CO) n may be reacted with halogen in advance, and then a phosphine compound may be used in combination. The transition metal-phosphine complex is usually a mononuclear complex having one Rh atom in the complex, but it may be a multinuclear complex having two or more Rh atoms.
【0026】[0026]
【実施例】以下に実施例を挙げて本発明を詳細に説明す
るが、本発明はこれらによって限定されるものではな
い。なお、以下の数値等の測定には次の機器を用いた。 核磁気共鳴スペクトル(NMR) EX−270(日本
電子製) 内部標準物質 1H:テトラメチルシラン 外部標準物質 31P:85%リン酸 光学純度 GC−15Aガスクロマトグラフィー(島津
製作所製) カラム:キラルキャピラリーカラム CHROMPACK β−236M 化学純度 日立−263−30ガスクロマトグラフィー
(日立製作所製) 旋光度 DIP−360(日本分光工業社製) また、使用した試薬の製造会社の略号の意味は以下のと
おりである。 和光=和光純薬工業株式会社 東京=東京化成工業株式会社 アルド=アルドリッチ・ジャパン・インク ナカライ=ナカライテスク株式会社The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. The following equipment was used for the measurement of the following numerical values and the like. Nuclear magnetic resonance spectrum (NMR) EX-270 (manufactured by JEOL Ltd.) Internal standard substance 1 H: Tetramethylsilane External standard substance 31 P: 85% phosphoric acid Optical purity GC-15A Gas chromatography (manufactured by Shimadzu Corporation) Column: Chiral Capillary column CHROMPACK β-236M Chemical purity Hitachi-263-30 Gas chromatography (manufactured by Hitachi, Ltd.) Optical rotation DIP-360 (manufactured by JASCO Corporation) The abbreviations of the manufacturers of the reagents used are as follows. . Wako = Wako Pure Chemical Industries, Ltd. Tokyo = Tokyo Chemical Industry Co., Ltd. Aldo = Aldrich Japan Inc. Nakarai = Nakarai Tesque Co., Ltd.
【0027】実施例1 (R)−2−ジフェニルホスフィノ−1,1′−ビナフ
タレン−2′−イルオキシ((S)−1,1′−ビナフ
タレン−2,2′−イルオキシ)ホスフィンの合成: (1)(S)−2,2′−ビス(トリフルオロメタンス
ルホニルオキシ)−1,1′−ビナフチルの合成:10
0mlのフラスコに塩化メチレン26ml、(S)−1,
1′−ビ−2−ナフトール(三菱瓦斯化学(株)製)5
g(17.4mmol)、2,6−ルチジン(東京)5.5
8g(52.2mmol)および4−ジメチルアミノピリジ
ン(和光)0.955g(7.83mmol)を溶解し、こ
の溶液中に0℃にてトリフルオロメタンスルホン酸無水
物(和光)14.7g(52.2mmol)を加え、室温で
23時間攪拌下に反応させた。反応終了後、溶媒を留去
した後、残渣を塩化メチレンを展開溶媒とするシリカゲ
ルカラムクロマトグラフィーで精製し、9.56gの
(S)−2,2′−ビス(トリフルオロメタンスルホニ
ルオキシ)−1,1′−ビナフチルを得た。収率100
%。Example 1 Synthesis of (R) -2-diphenylphosphino-1,1'-binaphthalen-2'-yloxy ((S) -1,1'-binaphthalen-2,2'-yloxy) phosphine: (1) Synthesis of (S) -2,2'-bis (trifluoromethanesulfonyloxy) -1,1'-binaphthyl: 10
26 ml of methylene chloride in a 0 ml flask, (S) -1,
1'-bi-2-naphthol (manufactured by Mitsubishi Gas Chemical Co., Inc.) 5
g (17.4 mmol), 2,6-lutidine (Tokyo) 5.5
8 g (52.2 mmol) and 4-dimethylaminopyridine (Wako) 0.955 g (7.83 mmol) were dissolved, and trifluoromethanesulfonic anhydride (Wako) 14.7 g (52. 2 mmol) was added, and the mixture was reacted at room temperature for 23 hours with stirring. After completion of the reaction, the solvent was distilled off, and the residue was purified by silica gel column chromatography using methylene chloride as a developing solvent to obtain 9.56 g of (S) -2,2'-bis (trifluoromethanesulfonyloxy) -1. , 1'-binaphthyl was obtained. Yield 100
%.
【0028】(2)2−オキソジフェニルホスフィノ−
2′−トリフルオロメタンスルホニルオキシ−1,1′
−ビナフチルの合成:100mlの4つ口フラスコに、ア
ルゴン気流下で(1)で調製した(S)−2,2′−ビ
ス(トリフルオロメタンスルホニルオキシ)−1,1′
−ビナフチル2.74g(4.98mmol)とジフェニル
ホスフィンオキシド(東京)1.99g(9.82mmo
l)をジメチルスルホキシド20mlに溶解し、この溶液
中に酢酸パラジウム(和光)110mg(0.491mmo
l)、エチルジイソプロピルアミン(アルド)5.1ml
および蟻酸ナトリウム(ナカライ)33mg(0.491
mmol)を加えて、室温で20分攪拌した。次に、溶液を
90℃で19時間攪拌した後室温に戻し、エーテル25
0mlと水150mlを加えて攪拌し分液した。分液後、有
機層を125mlの水で4回洗浄し、次に5%の希塩酸1
25mlで2回、50mlの水で2回、飽和炭酸水素ナトリ
ウム水溶液125mlで1回、最後に、飽和食塩水125
mlで洗浄した。得られた有機層を無水硫酸マグネシウム
で乾燥し、溶媒を留去した後、残渣をトルエン/アセト
ニトリル=3/1混合液(溶媒比、以下同様)を展開溶
媒とするシリカゲルカラムクロマトグラフィーにより精
製することにより、標記化合物を2.51g得た。収率
83%。(2) 2-oxodiphenylphosphino-
2'-trifluoromethanesulfonyloxy-1,1 '
-Synthesis of binaphthyl: (S) -2,2'-bis (trifluoromethanesulfonyloxy) -1,1 'prepared in (1) under a stream of argon in a 100 ml four-necked flask.
-Binaphthyl 2.74 g (4.98 mmol) and diphenylphosphine oxide (Tokyo) 1.99 g (9.82 mmo)
l) was dissolved in 20 ml of dimethyl sulfoxide, and 110 mg of palladium acetate (Wako) (0.491 mmo) was added to this solution.
l), ethyldiisopropylamine (ald) 5.1 ml
And sodium formate (Nacalai) 33 mg (0.491
mmol) was added and the mixture was stirred at room temperature for 20 minutes. The solution was then stirred at 90 ° C. for 19 hours and then allowed to come to room temperature and washed with ether 25
0 ml and 150 ml of water were added, and the mixture was stirred and separated. After separation, the organic layer was washed 4 times with 125 ml of water and then 5% diluted hydrochloric acid 1
25 ml twice, 50 ml water twice, saturated aqueous sodium hydrogen carbonate solution 125 ml once, and finally saturated saline solution 125
Washed with ml. The obtained organic layer is dried over anhydrous magnesium sulfate, the solvent is distilled off, and the residue is purified by silica gel column chromatography using a toluene / acetonitrile = 3/1 mixed solution (solvent ratio, the same applies below) as a developing solvent. Thus, 2.51 g of the title compound was obtained. Yield 83%.
【0029】(3)2−ジフェニルホスフィノ−2′−
ヒドロキシ−1,1′−ビナフチルの合成:50mlの3
つ口フラスコに2−オキソジフェニルホスフィノ−2′
−トリフルオロメタンスルホニルオキシ−1,1′−ビ
ナフチル400mg(0.664mmol)をキシレン22ml
に溶解させ、この中にトリエチルアミン(和光)1.2
1g(12mmol)とトリクロロシラン(アルド)1.6
2g(12mmol)を加えた。この混合液を120℃で1
7時間攪拌した。反応液の温度を室温まで戻した後、3
5%の水酸化ナトリウム4.4mlを注意深く加え、更に
2時間攪拌した後分液した。分液後、有機層を30mlの
飽和食塩水で2回洗浄した後、無水硫酸マグネシウムで
乾燥し、溶媒を減圧下留去することによって粗生成物を
得た。この粗生成物をテトラヒドロフラン7mlに溶解
し、この中に、水酸化リチウム(和光)335mg(7.
98mmol)を2.4mlの水に溶かした水溶液を加え、室
温で15時間攪拌した。エーテル50mlと5%希塩酸1
5mlを加えて分液し、有機層を水で2回洗浄してから無
水硫酸マグネシウムで乾燥し、溶媒を留去した後、残渣
をヘキサン/酢酸エチル=5/1の混合液を展開溶媒と
するシリカゲルカラムクロマトグラフィーで精製するこ
とにより標記化合物153mgを得た。収率51%。(3) 2-diphenylphosphino-2'-
Synthesis of hydroxy-1,1'-binaphthyl: 50 ml of 3
2-oxodiphenylphosphino-2 'in a two-necked flask
-Trifluoromethanesulfonyloxy-1,1'-binaphthyl 400 mg (0.664 mmol) xylene 22 ml
Dissolved in triethylamine (Wako) 1.2
1 g (12 mmol) and trichlorosilane (ald) 1.6
2 g (12 mmol) was added. This mixture at 120 ℃ 1
Stir for 7 hours. After returning the temperature of the reaction solution to room temperature, 3
4.4 ml of 5% sodium hydroxide was carefully added, and the mixture was further stirred for 2 hours and then separated. After liquid separation, the organic layer was washed twice with 30 ml of saturated saline and then dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. This crude product was dissolved in tetrahydrofuran (7 ml), and lithium hydroxide (Wako) 335 mg (7.
An aqueous solution prepared by dissolving 98 mmol) in 2.4 ml of water was added, and the mixture was stirred at room temperature for 15 hours. 50 ml ether and 1% 5% dilute hydrochloric acid
5 ml was added for liquid separation, the organic layer was washed twice with water, dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was mixed with hexane / ethyl acetate = 5/1 as a developing solvent. Purification by silica gel column chromatography described above gave 153 mg of the title compound. Yield 51%.
【0030】(4)(S)−1,1′−ビナフタレン−
2,2′−ジイルオキシシクロホスフィンの合成:アル
ゴン気流下、50mlの還流器をつけたフラスコに(S)
−1,1′−ビ−2−ナフトール(三菱瓦斯化学(株)
製)4.94g(17.3mmol)と三塩化リン(和光)
113g(0.83mol)を加え、4時間加熱還流した
後、室温に戻し未反応の三塩化リンは減圧下に留去して
白色結晶の標記化合物5.56gを得た。収率92%。(4) (S) -1,1'-Binaphthalene-
Synthesis of 2,2'-diyloxycyclophosphine: under a stream of argon, in a flask equipped with a 50 ml reflux condenser (S).
-1,1'-Bi-2-naphthol (Mitsubishi Gas Chemical Co., Ltd.)
Manufactured) 4.94 g (17.3 mmol) and phosphorus trichloride (Wako)
After adding 113 g (0.83 mol) and heating under reflux for 4 hours, the temperature was returned to room temperature and unreacted phosphorus trichloride was distilled off under reduced pressure to obtain 5.56 g of the title compound as white crystals. Yield 92%.
【0031】(5)(R)−2−ジフェニルホスフィノ
−1,1′−ビナフタレン−2′−イルオキシ((S)
−1,1′−ビナフタレン−2,2′−ジイルオキシ)
ホスフィンの合成:100mlのフラスコに(R)−2−
ジフェニルホスフィノ−2′−ヒドロキシ−1,1′−
ビナフチル430mg(0.946mmol)および(S)−
1,1′−ビナフト−2,2′−イルオキシクロロホス
フィン662mg(1.89mmol)をエーテル30mlに溶
解し、この中に0℃にてトリエチルアミン191mg
(1.89mmol)を加え、室温で15時間攪拌した後、
20mlの水を加えて反応を停止させた。分液後得られた
有機層を無水硫酸マグネシウムで乾燥し、溶媒を留去し
粗生成物を得た。このものを、ヘキサン/ジクロロメタ
ン=1/1の混合液を展開溶媒とするシリカゲルカラム
クロマトグラフィーで精製して(R)−2−ジフェニル
ホスフィノ−1,1′−ビナフタレン−2′−イルオキ
シ((S)−1,1′−ビナフタレン−2,2′−ジイ
ルオキシ)ホスフィン(以下、(R,S)−BINAP
HOSという)を白色結晶として712mg得た。収率9
8%。31 P-NMR(CDCl3)δ:−14.6(d,J=29.0Hz), 144.7(d,J=2
9.0Hz)(5) (R) -2-diphenylphosphino-1,1'-binaphthalen-2'-yloxy ((S)
-1,1'-Binaphthalene-2,2'-diyloxy)
Synthesis of phosphine: (R) -2-in a 100 ml flask
Diphenylphosphino-2'-hydroxy-1,1'-
Binaphthyl 430 mg (0.946 mmol) and (S)-
662 mg (1.89 mmol) of 1,1′-binaphtho-2,2′-yloxychlorophosphine was dissolved in 30 ml of ether, and 191 mg of triethylamine was added thereto at 0 ° C.
(1.89 mmol) was added and after stirring at room temperature for 15 hours,
The reaction was stopped by adding 20 ml of water. The organic layer obtained after liquid separation was dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a crude product. This product was purified by silica gel column chromatography using a mixed solution of hexane / dichloromethane = 1/1 as a developing solvent to obtain (R) -2-diphenylphosphino-1,1′-binaphthalen-2′-yloxy (( S) -1,1′-Binaphthalene-2,2′-diyloxy) phosphine (hereinafter (R, S) -BINAP
712 mg was obtained as white crystals. Yield 9
8%. 31 P-NMR (CDCl 3 ) δ: −14.6 (d, J = 29.0Hz), 144.7 (d, J = 2
(9.0Hz)
【0032】実施例2 (R)−2−(ジフェニルホスフィノ)−1,1′−ビ
ナフタレン−2′−イルオキシ((R)−1,1′−ビ
ナフタレン−2,2′−ジイルオキシ)ホスフィンの合
成:100mlのフラスコにエーテル30mlを加え、これ
に(R)−2−ジフェニルホスフィノ−2′−ヒドロキ
シ−1,1′−ビナフチル209mg(0.46mmol)と
(R)−1,1′−ビナフタレン−2,2′−ジイルオ
キシクロロホスフィン322mg(0.92mmol)を溶解
させた。この溶液に0℃にてトリエチルアミン191mg
(1.89mmol)を加えて、実施例1(5)と同様に操
作し、淡黄色固体である標記化合物(以下、(R,R)
−BINAPHOSという)を353mg得た。収率9
6.3%。31 P-NMR(CDCl3)δ:−18.0(d,J=9.2Hz), 140.5(d,J=9.2
Hz)Example 2 of (R) -2- (diphenylphosphino) -1,1'-binaphthalen-2'-yloxy ((R) -1,1'-binaphthalene-2,2'-diyloxy) phosphine Synthesis: To a 100 ml flask was added 30 ml of ether, and 209 mg (0.46 mmol) of (R) -2-diphenylphosphino-2'-hydroxy-1,1'-binaphthyl and (R) -1,1'- 322 mg (0.92 mmol) of binaphthalene-2,2'-diyloxychlorophosphine were dissolved. 191 mg of triethylamine in this solution at 0 ° C
(1.89 mmol) was added, and the same operation as in Example 1 (5) was conducted to give the title compound as a pale yellow solid (hereinafter, (R, R)).
-BINAPHOS) was obtained. Yield 9
6.3%. 31 P-NMR (CDCl 3 ) δ: -18.0 (d, J = 9.2Hz), 140.5 (d, J = 9.2
Hz)
【0033】実施例3 (R)−2−(ジフェニルホスフィノ)−1,1′−ビ
ナフタレン−2′−イルオキシ(ジフェノキシ)ホスフ
ィンの合成:(S)−1,1′−ビナフタレン−2,
2′−ジイルオキシクロロホスフィンの代わりにクロロ
ジフェノキシホスフィンを用いた以外は実施例1(5)
と同様の操作を行って、淡黄色固体の標記化合物(以
下、(R)−Ph−BINAPHOSという)を収率7
7%で得た。31 P-NMR(CDCl3)δ:−10.6(d,J=13.7Hz), 129.2(d,J=1
3.7Hz)Example 3 Synthesis of (R) -2- (diphenylphosphino) -1,1'-binaphthalen-2'-yloxy (diphenoxy) phosphine: (S) -1,1'-binaphthalene-2,
Example 1 (5) except that chlorodiphenoxyphosphine was used instead of 2'-diyloxychlorophosphine.
The title compound (hereinafter referred to as (R) -Ph-BINAPHOS) as a pale yellow solid is obtained in a yield of 7
Obtained at 7%. 31 P-NMR (CDCl 3 ) δ: -10.6 (d, J = 13.7Hz), 129.2 (d, J = 1
(3.7Hz)
【0034】実施例4 (R)−2−(ジ−(3,5−キシリル)ホスフィノ)
−1,1′−ビナフタレン−2′−イルオキシ((S)
−1,1′−ビナフタレン−2,2′−イルオキシ)ホ
スフィンの合成:100mlのフラスコにエーテル30ml
を加え、これに(R)−2−(ジ−(3,5−キシリ
ル)ホスフィノ−2′−ヒドロキシ−1,1′−ビナフ
チルを用いた以外は実施例1(5)と同様な操作を行っ
て、淡黄色固体の標記化合物(以下(R,S)−Me−
BINAPHOSという)を収率98%で得た。31 P-NMR(CDCl3)δ:−12.4(d,J=32.0Hz), 145.5(d)Example 4 (R) -2- (di- (3,5-xylyl) phosphino)
-1,1'-Binaphthalen-2'-yloxy ((S)
Synthesis of -1,1'-binaphthalene-2,2'-yloxy) phosphine: 30 ml ether in 100 ml flask
And the same procedure as in Example 1 (5) except that (R) -2- (di- (3,5-xylyl) phosphino-2′-hydroxy-1,1′-binaphthyl was used. The pale yellow solid of the title compound (hereinafter (R, S) -Me-
BINAPHOS) was obtained with a yield of 98%. 31 P-NMR (CDCl 3 ) δ: -12.4 (d, J = 32.0Hz), 145.5 (d)
【0035】実施例5 Rh−((R)−Ph−BINAPHOS)(aca
c)の合成:20mlのシュレンク管の中に、実施例3の
(R)−Ph−BINAPHOS17mg(0.025mm
ol)とRh(CO)2(acac)(acacはアセトセ
トナートを示す。以下同様)(アルド)6.5mg(0.
025mmol)を入れて、塩化メチレン5mlで溶解する。
反応液を室温で5分攪拌した後、減圧下溶媒を留去して
Rh((R)−Ph−BINAPHOS)(acac)
を黄色固体として22mg得た。収率100%。31 P-NMR(CDCl3)δ:51.1(dd,Jp-p=82.4Hz,JRh-p=174.0H
z),138.8(dd,JRh-p=328.1Hz)Example 5 Rh-((R) -Ph-BINAPHOS) (aca
Synthesis of c): 17 mg (0.025 mm) of (R) -Ph-BINAPHOS of Example 3 in a 20 ml Schlenk tube.
ol) and Rh (CO) 2 (acac) (acac represents acetosetonate. The same applies hereinafter) (ald) 6.5 mg (0.
(025 mmol), and dissolve with 5 ml of methylene chloride.
After stirring the reaction solution at room temperature for 5 minutes, the solvent was distilled off under reduced pressure to remove Rh ((R) -Ph-BINAPHOS) (acac).
22 mg was obtained as a yellow solid. Yield 100%. 31 P-NMR (CDCl 3 ) δ: 51.1 (dd, J pp = 82.4Hz, J Rh-p = 174.0H
z), 138.8 (dd, J Rh-p = 328.1Hz)
【0036】実施例6 Rh((R,S)−BINAPHOS)(acac)の
合成:実施例5の(R)−Ph−BINAPHOSの代
わりに(R,S)−BINAPHOSを用いる以外は実
施例5と同様に操作をしてRh((R,S)−BINA
PHOS)(acac)を63mg得た。収率99%。31 P-NMR(CDCl3)δ:48.3(dd,Jp-p=83.9Hz,JRh-p=174.0H
z),161.8(dd,JRh-p=331.1Hz)Example 6 Synthesis of Rh ((R, S) -BINAPHOS) (acac): Example 5 except that (R, S) -BINAPHOS was used instead of (R) -Ph-BINAPHOS in Example 5. Perform the same operation as for Rh ((R, S) -BINA
PHOS) (acac) was obtained at 63 mg. Yield 99%. 31 P-NMR (CDCl 3 ) δ: 48.3 (dd, J pp = 83.9Hz, J Rh-p = 174.0H
z), 161.8 (dd, J Rh-p = 331.1Hz)
【0037】実施例7 Rh((R,R)−BINAPHOS)(acac)の
合成:実施例5の(R)−Ph−BINAPHOSの代
わりに(R,R)−BINAPHOSを用いる以外は実
施例5と同様に操作をしてRh((R,R)−BINA
PHOS)(acac)を63mg得た。収率99%。31 P-NMR(CDCl3)δ:51.9(dd,Jp-p=80.8Hz,JRh-p=178.4H
z),152.5(dd,JRh-p=335.1Hz)Example 7 Synthesis of Rh ((R, R) -BINAPHOS) (acac): Example 5 except that (R, R) -BINAPHOS was used in place of (R) -Ph-BINAPHOS in Example 5. Perform the same operation as for Rh ((R, R) -BINA
PHOS) (acac) was obtained at 63 mg. Yield 99%. 31 P-NMR (CDCl 3 ) δ: 51.9 (dd, J pp = 80.8Hz, J Rh-p = 178.4H
z), 152.5 (dd, J Rh-p = 335.1Hz)
【0038】実施例8 Rh((R,S)−Me−BINAPHOS)(aca
c)の合成:実施例5の(R)−Ph−BINAPHO
Sの代わりに(R,S)−Me−BINAPHOSを用
いる以外は実施例5と同様に操作をしてRh((R,
S)−Me−BINAPHOS)(acac)を37mg
得た。収率99%。31 P-NMR(CDCl3)δ:48.8(dd,Jp-p=82.4Hz,JRh-p=172.4H
z),160.9(dd,JRh-p=332.6Hz)Example 8 Rh ((R, S) -Me-BINAPHOS) (aca
Synthesis of c): (R) -Ph-BINAPHO of Example 5.
Except that (R, S) -Me-BINAPHOS is used instead of S, the same operation as in Example 5 is performed to perform Rh ((R,
S) -Me-BINAPHOS) (acac) 37 mg
Obtained. Yield 99%. 31 P-NMR (CDCl 3 ) δ: 48.8 (dd, J pp = 82.4Hz, J Rh-p = 172.4H
z), 160.9 (dd, J Rh-p = 332.6Hz)
【0039】参考例1 酢酸ビニルの不斉ヒドロホルミル化反応:50mlのオー
トクレーブに酢酸ビニル(和光)1.301g(15.
13mmol)、触媒前駆体としてRh(CO)2(aca
c)9.8mg(0.0378mmol)、光学活性ホスフィ
ンとして(R,S)−BINAPHOS 58mg(0.
0755mmol)、ベンゼン14mlを加え、水素圧50a
tm、一酸化炭素圧50atmで、60℃で112時間
攪拌した。酢酸ビニルの転化率の測定および生成物の分
析はガスクロマトグラフィー(10% SE−30 o
n Chromosorb W 80−100 mes
h packed in a 5mm×2m glass
column)を用い、光学純度は光学活性ガスクロ
マトグラフィー(Astec Chiraldex B
−PH)により決定した。その結果、本反応で生成した
化合物は2−アセトキシプロパナール90%と3−アセ
トキシプロパナール10%の混合物であり、転化率は9
8%であった。次いで、2−アセトキシプロパナールを
蒸留し、このものの光学純度を測定したところ90%e
eであった。次にこのものをジョーンズ酸化して2−ア
セトキシプロピオン酸に導き、旋光度を測定したとこ
ろ、このものは(S)−(−)−2−アセトキシプロピ
オン酸であることが確認された。Reference Example 1 Asymmetric hydroformylation reaction of vinyl acetate: 1.301 g of vinyl acetate (Wako) in a 50 ml autoclave (15.
13 mmol) and Rh (CO) 2 (aca as a catalyst precursor
c) 9.8 mg (0.0378 mmol), as an optically active phosphine (R, S) -BINAPHOS 58 mg (0.
(0755 mmol) and 14 ml of benzene are added, and the hydrogen pressure is 50a.
The mixture was stirred at 60 ° C. for 112 hours under tm and carbon monoxide pressure of 50 atm. The conversion of vinyl acetate and the analysis of the product were measured by gas chromatography (10% SE-30 o).
n Chromosorb W 80-100 mes
h packed in a 5mm × 2m glass
column), and the optical purity is determined by optically active gas chromatography (Astec Chiraldex B).
-PH). As a result, the compound produced in this reaction was a mixture of 90% 2-acetoxypropanal and 10% 3-acetoxypropanal, and the conversion rate was 9%.
It was 8%. Then, 2-acetoxypropanal was distilled and the optical purity of this was measured to be 90% e.
It was e. Next, this product was subjected to Jones oxidation to 2-acetoxypropionic acid, and the optical rotation was measured. As a result, it was confirmed that this product was (S)-(−)-2-acetoxypropionic acid.
【0040】参考例2 酢酸ビニルの不斉ヒドロホルミル化反応:触媒としてR
h((R,R)−BINAPHOS)(acac)を用
い、50℃、37時間で反応させた以外は参考例1と同
様に操作して、2−アセトキシプロパナール92%と3
−アセトキシプロパナール8%の混合物を得た。転化率
46%。参考例1と同様にして蒸留した2−アセトキシ
プロパナールの光学純度は73%eeであった。次にこ
のものをジョーンズ酸化して2−アセトキシプロピオン
酸に導き、旋光度を測定したところ、このものは(S)
−(−)−2−アセトキシプロピオン酸であることが確
認された。Reference Example 2 Asymmetric Hydroformylation of Vinyl Acetate: R as Catalyst
Using the same procedure as in Reference Example 1 except that h ((R, R) -BINAPHOS) (acac) was reacted at 50 ° C. for 37 hours, 92% of 2-acetoxypropanal and 3%
A mixture of 8% acetoxypropanal was obtained. Conversion rate is 46%. The optical purity of 2-acetoxypropanal distilled in the same manner as in Reference Example 1 was 73% ee. Next, this product was subjected to Jones oxidation to 2-acetoxypropionic acid, and the optical rotation was measured.
It was confirmed to be-(-)-2-acetoxypropionic acid.
【0041】参考例3 スチレンのヒドロホルミル化反応:50mgのオートクレ
ーブにスチレン(ナカライ)3.06g(29.4mmo
l)、Rh(CO)2(acac)3.7mg(0.0143
mmol)、(S,R)−BINAPHOS 44mg(0.
0573mmol)、重ベンゼン1mlを加え、50atmの
水素と50atmの一酸化炭素を加えて、60℃で43
時間攪拌した。反応終了後、反応液を室温まで戻し、加
圧ガスを除いた後に反応混合物を直接1H−NMRで分
析したところ、スチレンの転化率は99%以上であり、
生成物である2−フェニルプロパナール88%と3−フ
ェニルプロパナール12%の混合物を1.273g得
た。なお、ほかの生成物は全く見られなかった。参考例
1と同様にして2−フェニルプロピオン酸に導いて光学
純度を測定したところ、94%eeの(S)−(+)−
2−フェニルプロピオン酸であることが確認された。Reference Example 3 Hydroformylation reaction of styrene: 3.06 g (29.4 mmo) of styrene (Nacalai) in a 50 mg autoclave.
l), Rh (CO) 2 (acac) 3.7 mg (0.0143)
mmol), (S, R) -BINAPHOS 44 mg (0.
(0573 mmol) and 1 ml of heavy benzene, 50 atm of hydrogen and 50 atm of carbon monoxide are added, and the mixture is heated to 43 at 60 ° C.
Stir for hours. After completion of the reaction, the reaction solution was returned to room temperature, the pressurized gas was removed, and the reaction mixture was directly analyzed by 1 H-NMR. As a result, the conversion rate of styrene was 99% or more,
1.273 g of a product mixture of 2-phenylpropanal 88% and 3-phenylpropanal 12% was obtained. No other products were found. When the optical purity was measured by introducing it into 2-phenylpropionic acid in the same manner as in Reference Example 1, (S)-(+)-of 94% ee was obtained.
It was confirmed to be 2-phenylpropionic acid.
【0042】[0042]
【発明の効果】本発明の遷移金属−ホスフィン錯体を不
斉合成の触媒として使用すれば、所望の絶対配置の目的
物を高い光学純度で高収率にて製造することができる。EFFECTS OF THE INVENTION By using the transition metal-phosphine complex of the present invention as a catalyst for asymmetric synthesis, it is possible to produce a desired product having a desired absolute configuration with high optical purity and high yield.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成6年3月11日[Submission date] March 11, 1994
【手続補正1】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0007[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0007】光学活性な第3級ホスファイトを配位子と
する錯体としては、例えばテトラヘドロン・アシンメト
リー(Tetrahedron Asymmetr
y)、第3巻、583〜586頁、1992年に、光学
活性なBINAP構造を有するビス(トリアリールホス
ファイト)が記載されており、このものを配位子とする
ロジウム錯体を用いた酢酸ビニルの不斉ヒドロホルミル
化反応が記載されている。Examples of the complex having an optically active tertiary phosphite as a ligand include, for example, tetrahedron asymmetry (Tetrahedron Asymmetr).
y), Vol. 3, pp. 583-586, 1992 describes a bis (triarylphosphite) having an optically active BINAP structure. Acetic acid using a rhodium complex having this as a ligand is described. The asymmetric hydroformylation reaction of vinyl has been described.
【手続補正2】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0019[Correction target item name] 0019
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0019】(式中、Tfはトリフルオロメタンスルホ
ニル基を示し、R1、R2、R3およびR4は前記と同
じものを示す) すなわち、テトラヘドロン・レターズ(Tetrahe
dron Letters)、第31巻、6321〜6
324頁、1990年に記載の方法に準じて、1,1−
ビ−2−ナフトール(3)にトリフルオロメタンスルホ
ン酸無水物(4)を反応せしめて2,2′−ビス(トリ
フルオロメタンスルホニルオキシ)−1,1′−ビナフ
チル(5)となし、これにパラジウム触媒の存在下、ホ
スフィンオキシド(6)を反応せしめて2−ホスフィニ
ル−2′−トリフルオロメタンスルホニルオキシ−1,
1′−ビナフチル(7)となし、次いでこれをトリエチ
ルアミンの存在下還元した後、加水分解して2−ホスフ
ィノ−2′−ヒドロキシ−1,1′−ビナフチル(8)
となし、更にこれにクロロホスフィン(9)をトリエチ
ルアミンの存在下反応せしめれば、本発明のホスフィン
化合物(1)が製造される。(In the formula, T f represents a trifluoromethanesulfonyl group, and R 1 , R 2 , R 3 and R 4 are the same as the above), that is, tetrahedron letters (Tetrahe)
dron Letters), Volume 31, 6321-6
324, 1,1 according to the method described in 1990
Bi-2-naphthol (3) was reacted with trifluoromethanesulfonic anhydride (4) to give 2,2'-bis (trifluoromethanesulfonyloxy) -1,1'-binaphthyl (5), which was then treated with palladium. In the presence of a catalyst, phosphine oxide (6) is reacted to give 2-phosphinyl-2'-trifluoromethanesulfonyloxy-1,
1'-binaphthyl (7), which was then reduced in the presence of triethylamine and then hydrolyzed to give 2-phosphino-2'-hydroxy-1,1'-binaphthyl (8).
By further reacting this with chlorophosphine (9) in the presence of triethylamine, the phosphine compound (1) of the present invention is produced.
【手続補正3】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0021[Correction target item name] 0021
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0021】また、本発明の遷移金属−ホスフィン錯体
(2)は、公知の方法に準じて製造することができる。
以下、ロジウムを例にして説明する。例えば、J.A
m.Chem.Soc.,93,3089(1971)
に記載の方法に従って、[Rh(COD)(Cl)]2
(COD:1,5−シクロオクタジエン)およびAgC
lO4から製造した〔Rh(COD)2〕ClO4と本
発明のホスフィン化合物(1)(L)を反応せしめれば
〔Rh(L)(COD)〕ClO4が得らる。The transition metal-phosphine complex (2) of the present invention can be produced according to a known method.
Hereinafter, rhodium will be described as an example. For example, J. A
m. Chem. Soc. , 93 , 3089 (1971)
[Rh (COD) (Cl)] 2 according to the method described in 1.
(COD: 1,5-cyclooctadiene) and AgC
If Seshimere reaction was prepared from lO 4 [Rh (COD) 2] ClO 4 and phosphine compound of the present invention (1) (L) [Rh (L) (COD)] ClO 4 is Tokuraru.
【手続補正4】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0027[Name of item to be corrected] 0027
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0027】実施例1 (R)−2−ジフェニルホスフィノ−1,1′−ビナフ
タレン−2′−イルオキシ((S)−1,1′−ビナフ
タレン−2,2′−ジイルジオキシ)ホスフィンの合
成: (1)(R)−2,2′−ビス(トリフルオロメタンス
ルホニルオキシ)−1,1′−ビナフチルの合成:10
0mlのフラスコに塩化メチレン26ml、(R)−
1,1′−ビ−2−ナフトール(三菱瓦斯化学(株)
製)5g(17.4mmol)、2,6−ルチジン(東
京)5.58g(52.2mmol)および4−ジメチ
ルアミノピリジン(和光)0.955g(7.83mm
ol)を溶解し、この溶液中に0℃にてトリフルオロメ
タンスルホン酸無水物(和光)14.7g(52.2m
mol)を加え、室温で23時間撹拌下に反応させた。
反応終了後、溶媒を留去した後、残渣を塩化メチレンを
展開溶媒とするシリカゲルカラムクロマトグラフィーで
精製し、9.56gの(R)−2,2′−ビス(トリフ
ルオロメタンスルホニルオキシ)−1,1′−ビナフチ
ルを得た。収率100%。Example 1 Synthesis of (R) -2-diphenylphosphino-1,1'-binaphthalen-2'-yloxy ((S) -1,1'-binaphthalene-2,2'-diyldioxy) phosphine: (1) Synthesis of (R) -2,2'-bis (trifluoromethanesulfonyloxy) -1,1'-binaphthyl: 10
26 ml of methylene chloride in a 0 ml flask, (R)-
1,1'-bi-2-naphthol (Mitsubishi Gas Chemical Co., Ltd.)
Made), 5 g (17.4 mmol), 2,6-lutidine (Tokyo) 5.58 g (52.2 mmol) and 4-dimethylaminopyridine (Wako) 0.955 g (7.83 mm).
ol) was dissolved, and 14.7 g (52.2 m) of trifluoromethanesulfonic anhydride (Wako) was dissolved in this solution at 0 ° C.
mol) was added, and the mixture was reacted at room temperature for 23 hours with stirring.
After completion of the reaction, the solvent was distilled off, and the residue was purified by silica gel column chromatography using methylene chloride as a developing solvent to obtain 9.56 g of (R) -2,2'-bis (trifluoromethanesulfonyloxy) -1. , 1'-binaphthyl was obtained. Yield 100%.
【手続補正5】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0028[Correction target item name] 0028
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0028】(2)(R)−2−ジフェニルホスフィニ
ル−2′−トリフルオロメタンスルホニルオキシ−1,
1′−ビナフチルの合成:100mlの4つ口フラスコ
に、アルゴン気流下で(1)で調製した(R)−2,
2′−ビス(トリフルオロメタンスルホニルオキシ)−
1,1′−ビナフチル2.74g(4.98mmol)
とジフェニルホスフィンオキシド(東京)1.99g
(9.82mmol)をジメチルスルホキシド20ml
に溶解し、この溶液中に酢酸パラジウム(和光)110
mg(0.491mmol)、1,4−ビス(ジフェニ
ルホスフィノ)ブタン210mg(0.491mmo
l)、エチルジイソプロピルアミン(アルド)5.1m
lおよび蟻酸ナトリウム(ナカライ)33mg(0.4
91mmol)を加えて、室温で20分撹拌した。次
に、溶液を90℃で19時間撹拌した後室温に戻し、エ
ーテル250mlと水150mlを加えて撹拌し分液し
た。分液後、有機層を125mlの水で4回洗浄し、次
に5%の希塩酸125mlで2回、50mlの水で2
回、飽和炭酸水素ナトリウム水溶液125mlで1回、
最後に、飽和食塩水125mlで洗浄した。得られた有
機層を無水硫酸マグネシウムで乾燥し、溶媒を留去した
後、残渣をトルエン/アセトニトリル=3/1混合液
(溶媒比、以下同様)を展開溶媒とするシリカゲルカラ
ムクロマトグラフィーにより精製することにより、標記
化合物を2.51g得た。収率83%。(2) (R) -2-diphenylphosphinyl-2'-trifluoromethanesulfonyloxy-1,
Synthesis of 1'-binaphthyl: (R) -2, prepared in (1) under a stream of argon in a 100 ml four-necked flask,
2'-bis (trifluoromethanesulfonyloxy)-
2.74 g (4.98 mmol) of 1,1'-binaphthyl
And diphenylphosphine oxide (Tokyo) 1.99g
(9.82 mmol) 20 ml of dimethyl sulfoxide
And palladium acetate (Wako) 110 in this solution.
mg (0.491 mmol), 1,4-bis (diphenylphosphino) butane 210 mg (0.491 mmo)
l), ethyldiisopropylamine (ald) 5.1 m
l and sodium formate (Nacalai) 33 mg (0.4
91 mmol) was added and the mixture was stirred at room temperature for 20 minutes. Next, the solution was stirred at 90 ° C. for 19 hours and then returned to room temperature, 250 ml of ether and 150 ml of water were added, and the mixture was stirred and separated. After separation, the organic layer was washed 4 times with 125 ml of water, then twice with 125 ml of 5% dilute hydrochloric acid and 2 times with 50 ml of water.
Once with 125 ml of saturated aqueous sodium hydrogen carbonate solution,
Finally, it was washed with 125 ml of saturated saline. The obtained organic layer is dried over anhydrous magnesium sulfate, the solvent is distilled off, and the residue is purified by silica gel column chromatography using a toluene / acetonitrile = 3/1 mixture (solvent ratio, the same applies below) as a developing solvent. Thus, 2.51 g of the title compound was obtained. Yield 83%.
【手続補正6】[Procedure correction 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0029[Name of item to be corrected] 0029
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0029】(3)(R)−2−ジフェニルホスフィノ
−2′−ヒドロキシ−1,1′−ビナフチルの合成:5
0mlの3つ口フラスコに(R)−2−ジフェニルホス
フィニル−2′−トリフルオロメタンスルホニルオキシ
−1,1′−ビナフチル400mg(0.664mmo
l)をキシレン22mlに溶解させ、この中にトリエチ
ルアミン(和光)1.21g(12mmol)とトリク
ロロシラン(アルド)1.62g(12mmol)を加
えた。この混合液を120℃で17時間攪拌した。反応
液の温度を室温まで戻した後、35%の水酸化ナトリウ
ム4.4mlを注意深く加え、更に2時間撹拌した後分
液した。分液後、有機層を30mlの飽和食塩水で2回
洗浄した後、無水硫酸マグネシウムで乾燥し、溶媒を減
圧下留去することによって粗生成物を得た。この粗生成
物をテトラヒドロフラン7mlに溶解し、この中に、水
酸化リチウム(和光)335mg(7.98mmol)
を2.4mlの水に溶かした水溶液を加え、室温で15
時間撹拌した。エーテル50mlと5%希塩酸15ml
を加えて分液し、有機層を水で2回洗浄してから無水硫
酸マグネシウムで乾燥し、溶媒を留去した後、残渣をヘ
キサン/酢酸エチル=5/1の混合液を展開溶媒とする
シリカゲルカラムクロマトグラフィーで精製することに
より標記化合物153mgを得た。収率51%。(3) Synthesis of (R) -2-diphenylphosphino-2'-hydroxy-1,1'-binaphthyl: 5
In a 0 ml three-necked flask, 400 mg (0.664 mmo) of (R) -2-diphenylphosphinyl-2′-trifluoromethanesulfonyloxy-1,1′-binaphthyl was added.
l) was dissolved in 22 ml of xylene, and 1.21 g (12 mmol) of triethylamine (Wako) and 1.62 g (12 mmol) of trichlorosilane (ald) were added thereto. The mixture was stirred at 120 ° C. for 17 hours. After returning the temperature of the reaction solution to room temperature, 4.4 ml of 35% sodium hydroxide was carefully added, and the mixture was further stirred for 2 hours and then separated. After liquid separation, the organic layer was washed twice with 30 ml of saturated saline and then dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. This crude product was dissolved in 7 ml of tetrahydrofuran, and 335 mg (7.98 mmol) of lithium hydroxide (Wako) was added to the solution.
Was added to 2.4 ml of water and added at room temperature for 15
Stir for hours. 50 ml of ether and 15 ml of 5% dilute hydrochloric acid
Was added to separate the layers, the organic layer was washed twice with water, dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was treated with a mixed solution of hexane / ethyl acetate = 5/1 as a developing solvent. Purification by silica gel column chromatography gave 153 mg of the title compound. Yield 51%.
【手続補正7】[Procedure Amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0030[Name of item to be corrected] 0030
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0030】(4)(S)−1,1′−ビナフタレン−
2,2′−ジイルジオキシクロロホスフィンの合成:ア
ルゴン気流下、50mlの還流器をつけたフラスコに
(S)−1,1′−ビ−2−ナフトール(三菱瓦斯化学
(株)製)4.94g(17.3mmol)と三塩化リ
ン(和光)113g(0.83mol)を加え、4時間
加熱還流した後、室温に戻し未反応の三塩化リンは減圧
下に留去して白色結晶の標記化合物5.56gを得た。
収率92%。(4) (S) -1,1'-Binaphthalene-
Synthesis of 2,2'-diyldioxychlorophosphine: (S) -1,1'-bi-2-naphthol (manufactured by Mitsubishi Gas Chemical Co., Inc.) 4 in a flask equipped with a 50 ml reflux condenser under an argon stream. After adding 94 g (17.3 mmol) and 113 g (0.83 mol) of phosphorus trichloride (Wako) and heating under reflux for 4 hours, the mixture was returned to room temperature and unreacted phosphorus trichloride was distilled off under reduced pressure to obtain white crystals. 5.56 g of the title compound was obtained.
Yield 92%.
【手続補正8】[Procedure Amendment 8]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0031[Correction target item name] 0031
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0031】(5)(R)−2−ジフェニルホスフィノ
−1,1′−ビナフタレン−2′−イルオキシ((S)
−1,1′−ビナフタレン−2,2′−ジイルジオキ
シ)ホスフィンの合成:100mlのフラスコに(R)
−2−ジフェニルホスフィノ−2′−ヒドロキシ−1,
1′−ビナフチル430mg(0.946mmol)お
よび(S)−1,1′−ビナフタレン−2,2′−ジイ
ルジオキシクロロホスフィン662mg(1.89mm
ol)をエーテル30mlに溶解し、この中に0℃にて
トリエチルアミン191mg(1.89mmol)を加
え、室温で15時間攪拌した後、20mlの水を加えて
反応を停止させた。分液後得られた有機層を無水硫酸マ
グネシウムで乾燥し、溶媒を留去し粗生成物を得た。こ
のものを、ヘキサン/ジクロロメタン=1/1の混合液
を展開溶媒とするシリカゲルカラムクロマトグラフィー
で精製して(R)−2−ジフェニルホスフィノ−1,
1′−ビナフタレン−2′−イルオキシ((S)−1,
1′−ビナフタレン−2,2′−ジイルジオキシ)ホス
フィン(以下、(R,S)−BINAPHOSという)
を白色結晶として712mg得た。収率98%。31 P−NMR(CDCl3)δ:−14.6(d,J
=29.0Hz),144.7(d,J=29.0H
z)(5) (R) -2-diphenylphosphino-1,1'-binaphthalen-2'-yloxy ((S)
Synthesis of -1,1'-binaphthalene-2,2'-diyldioxy) phosphine: (R) in a 100 ml flask.
-2-diphenylphosphino-2'-hydroxy-1,
430 mg (0.946 mmol) of 1'-binaphthyl and 662 mg (1.89 mm) of (S) -1,1'-binaphthalene-2,2'-diyldioxychlorophosphine.
ol) was dissolved in 30 ml of ether, 191 mg (1.89 mmol) of triethylamine was added thereto at 0 ° C., the mixture was stirred at room temperature for 15 hours, and then 20 ml of water was added to stop the reaction. The organic layer obtained after liquid separation was dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a crude product. This product was purified by silica gel column chromatography using a mixed solution of hexane / dichloromethane = 1/1 as a developing solvent to obtain (R) -2-diphenylphosphino-1,
1'-Binaphthalen-2'-yloxy ((S) -1,
1'-Binaphthalene-2,2'-diyldioxy) phosphine (hereinafter referred to as (R, S) -BINAPHOS)
712 mg was obtained as a white crystal. Yield 98%. 31 P-NMR (CDCl 3 ) δ: −14.6 (d, J
= 29.0 Hz), 144.7 (d, J = 29.0H)
z)
【手続補正9】[Procedure Amendment 9]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0032[Name of item to be corrected] 0032
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0032】実施例2 (R)−2−(ジフェニルホスフィノ)−1,1′−ビ
ナフタレン−2′−イルオキシ((R)−1,1′−ビ
ナフタレン−2,2′−ジイルジオキシ)ホスフィンの
合成:100mlのフラスコにエーテル30mlを加
え、これに(R)−2−ジフェニルホスフィノ−2′−
ヒドロキシ−1,1′−ビナフチル209mg(0.4
6mmol)と(R)−1,1′−ビナフタレン−2,
2′−ジイルジオキシクロロホスフィン322mg
(0.92mmol)を溶解させた。この溶液に0℃に
てトリエチルアミン191mg(1.89mmol)を
加えて、実施例1(5)と同様に操作し、淡黄色固体で
ある標記化合物(以下、(R,R)−BINAPHOS
という)を353mg得た。収率96.3%。31 P−NMR(CDCl3)δ:−18.0(d,J
=9.2Hz),140.5(d,J=9.2Hz)Example 2 of (R) -2- (diphenylphosphino) -1,1'-binaphthalen-2'-yloxy ((R) -1,1'-binaphthalene-2,2'-diyldioxy) phosphine Synthesis: To a 100 ml flask, 30 ml of ether was added, and (R) -2-diphenylphosphino-2'- was added to this.
Hydroxy-1,1'-binaphthyl 209 mg (0.4
6 mmol) and (R) -1,1′-binaphthalene-2,
322 mg of 2'-diyldioxychlorophosphine
(0.92 mmol) was dissolved. To this solution was added 191 mg (1.89 mmol) of triethylamine at 0 ° C., and the same operation as in Example 1 (5) was conducted to give the title compound as a pale yellow solid (hereinafter, (R, R) -BINAPHOS).
) Was obtained. Yield 96.3%. 31 P-NMR (CDCl 3 ) δ: -18.0 (d, J
= 9.2 Hz), 140.5 (d, J = 9.2 Hz)
【手続補正10】[Procedure Amendment 10]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0033[Correction target item name] 0033
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0033】実施例3 (R)−2−(ジフェニルホスフィノ)−1,1′−ビ
ナフタレン−2′−イルオキシ(ジフェノキシ)ホスフ
ィンの合成:(S)−1,1′−ビナフタレン−2,
2′−ジイルジオキシクロロホスフィンの代わりにクロ
ロジフェノキシホスフィンを用いた以外は実施例1
(5)と同様の操作を行って、淡黄色固体の標記化合物
(以下、(R)−Ph−BINAPHOSという)を収
率77%で得た。31 P−NMR(CDCl3)δ:−10.6(d,J
=13.7Hz),129.2(d,J=13.7H
z)Example 3 Synthesis of (R) -2- (diphenylphosphino) -1,1'-binaphthalen-2'-yloxy (diphenoxy) phosphine: (S) -1,1'-binaphthalene-2,
Example 1 except that chlorodiphenoxyphosphine was used instead of 2'-diyldioxychlorophosphine.
The same operation as in (5) was carried out to obtain the title compound as a pale yellow solid (hereinafter referred to as (R) -Ph-BINAPHOS) in a yield of 77%. 31 P-NMR (CDCl 3 ) δ: -10.6 (d, J
= 13.7 Hz), 129.2 (d, J = 13.7H)
z)
【手続補正11】[Procedure Amendment 11]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0034[Correction target item name] 0034
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0034】実施例4 (R)−2−(ジ−(3,5−キシリル)ホスフィノ)
−1,1′−ビナフタレン−2′−イルオキシ((S)
−1,1′−ビナフタレン−2,2′−ジイルジオキ
シ)ホスフィンの合成:100mlのフラスコにエーテ
ル30mlを加え、これに(R)−2−(ジ−(3,5
−キシリル)ホスフィノ−2′−ヒドロキシ−1,1′
−ビナフチルを用いた以外は実施例1(5)と同様な操
作を行って、淡黄色固体の標記化合物(以下(R,S)
−Me−BINAPHOSという)を収率98%で得
た。31 P−NMR(CDCl3)δ:−12.4(d,J
=32.0Hz),145.5(d)Example 4 (R) -2- (di- (3,5-xylyl) phosphino)
-1,1'-Binaphthalen-2'-yloxy ((S)
Synthesis of -1,1'-binaphthalene-2,2'-diyldioxy) phosphine: 30 ml of ether was added to a 100 ml flask, and (R) -2- (di- (3,5
-Xylyl) phosphino-2'-hydroxy-1,1 '
By the same procedure as in Example 1 (5) except that binaphthyl was used, the title compound as a pale yellow solid (hereinafter (R, S)) was used.
-Me-BINAPOS) was obtained with a yield of 98%. 31 P-NMR (CDCl 3 ) δ: -12.4 (d, J
= 32.0 Hz), 145.5 (d)
【手続補正12】[Procedure Amendment 12]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0035[Correction target item name] 0035
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0035】実施例5 Rh−((R)−Ph−BINAPHOS)(aca
c)の合成:20mlのシュレンク管の中に、実施例3
の(R)−Ph−BINAPHOS17mg(0.02
5mmol)とRh(CO)2(acac)(acac
はアセトアセトナートを示す。以下同様)(アルド)
6.5mg(0.025mmol)を入れて、塩化メチ
レン5mlで溶解する。反応液を室温で5分攪拌した
後、減圧下溶媒を留去してRh((R)−Ph−BIN
APHOS)(acac)を黄色固体として22mg得
た。収率100%。31 P−NMR(CDCl3)δ:51.1(dd,J
p−p=82.4Hz,JRh−p=174.0H
z), 138.8(dd,J
Rh−p=328.1Hz)Example 5 Rh-((R) -Ph-BINAPHOS) (aca
Synthesis of c): Example 3 in a 20 ml Schlenk tube.
17 mg (0.02) of (R) -Ph-BINAPHOS
5 mmol) and Rh (CO) 2 (acac) (acac
Indicates acetoacetonate. The same applies hereinafter) (Aldo)
Add 6.5 mg (0.025 mmol) and dissolve in 5 ml methylene chloride. After stirring the reaction solution at room temperature for 5 minutes, the solvent was distilled off under reduced pressure to remove Rh ((R) -Ph-BIN).
22 mg of APHOS) (acac) was obtained as a yellow solid. Yield 100%. 31 P-NMR (CDCl 3 ) δ: 51.1 (dd, J
pp = 82.4 Hz, J Rh-p = 174.0H
z), 138.8 (dd, J
Rh-p = 328.1 Hz)
【手続補正13】[Procedure Amendment 13]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0041[Correction target item name] 0041
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0041】参考例3 スチレンのヒドロホルミル化反応:50mlのオートク
レーブにスチレン(ナカライ)3.06g(29.4m
mol)、Rh(CO)2(acac)3.7mg
(0.0143mmol)、(S,R)−BINAPH
OS 44mg(0.0573mmol)、重ベンゼン
1mlを加え、50atmの水素と50atmの一酸化
炭素を加えて、60℃で43時間攪拌した。反応終了
後、反応液を室温まで戻し、加圧ガスを除いた後に反応
混合物を直接1H−NMRで分析したところ、スチレン
の転化率は99%以上であり、生成物である2−フェニ
ルプロパナール88%と3−フェニルプロパナール12
%の混合物を1.273g得た。なお、ほかの生成物は
全く見られなかった。参考例1と同様にして2−フェニ
ルプロピオン酸に導いて光学純度を測定したところ、9
4%eeの(S)−(+)−2−フェニルプロピオン酸
であることが確認された。Reference Example 3 Hydroformylation reaction of styrene: 3.06 g (29.4 m) of styrene (Nacalai) was added to a 50 ml autoclave.
mol), Rh (CO) 2 (acac) 3.7 mg
(0.0143 mmol), (S, R) -BINAPH
44 mg (0.0573 mmol) of OS and 1 ml of deuterated benzene were added, 50 atm of hydrogen and 50 atm of carbon monoxide were added, and the mixture was stirred at 60 ° C. for 43 hours. After the reaction was completed, the reaction solution was returned to room temperature, the pressurized gas was removed, and the reaction mixture was directly analyzed by 1 H-NMR. As a result, the conversion rate of styrene was 99% or more, and the product 2-phenylpro 88% Panard and 12-Phenylpropanal 12
% 1.73 g of a mixture was obtained. No other products were found. In the same manner as in Reference Example 1, the optical purity was measured by introducing it into 2-phenylpropionic acid.
It was confirmed to be (S)-(+)-2-phenylpropionic acid with 4% ee.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 // C07B 61/00 300 C07C 45/50 47/228 7188−4H (72)発明者 玉尾 京子 京都府京都市上京区河原町通丸太町上る出 水町262番地 ベル・メゾン鴨川303号 (72)発明者 真野 聡 京都府京都市左京区一乗寺築田町17番地 藤田マンション208 (72)発明者 雲林 秀徳 東京都大田区蒲田5丁目36番31号 高砂香 料工業株式会社総合研究所内 (72)発明者 富田 哲郎 東京都港区芝浦1丁目2番1号 三菱瓦斯 化学株式会社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location // C07B 61/00 300 C07C 45/50 47/228 7188-4H (72) Inventor Kyoko Tamao 262 Izumi-cho, Kawaramachi-dori, Logan-cho, Kamigyo-ku, Kyoto-shi, Kyoto Prefecture No. 303, Bell Maison Kamogawa (72) Inventor Satoshi Mano 17 Ichijoji-Kitatacho, Sakyo-ku, Kyoto-shi, Kyoto Prefecture Fujita Mansion 208 (72) Hidenori Unbayashi Tokyo 5-36-31 Kamata, Ota-ku, Tokyo Inside Takasago International Corporation (72) Inventor Tetsuro Tomita 1-2-1 Shibaura, Minato-ku, Tokyo Inside Mitsubishi Gas Chemical Co., Inc.
Claims (5)
原子または低級アルキル基で置換されていてもよいフェ
ニル基を示すか、R1とR2が共同して2価の炭化水素基
を示し、R3およびR4は同一または異なって、低級アル
キル基またはハロゲン原子、低級アルキル基もしくは低
級アルコキシ基で置換されていてもよいフェニル基を示
すか、R3とR4が共同して2価の炭化水素基を示す)で
表わされるホスフィン化合物。1. A compound represented by the general formula (1): (In the formula, R 1 and R 2 are the same or different and each represents a phenyl group which may be substituted with a halogen atom or a lower alkyl group, or R 1 and R 2 together form a divalent hydrocarbon group. R 3 and R 4 are the same or different and each represents a lower alkyl group or a phenyl group which may be substituted with a halogen atom, a lower alkyl group or a lower alkoxy group, or R 3 and R 4 jointly represent 2 Which represents a valent hydrocarbon group).
子とする遷移金属−ホスフィン錯体。2. A transition metal-phosphine complex having the phosphine compound according to claim 1 as a ligand.
ジウム、イリジウム、白金、コバルト、ニッケル及びチ
タンより選ばれたものである請求項2記載の遷移金属−
ホスフィン錯体。3. The transition metal according to claim 2, wherein the transition metal is selected from rhodium, ruthenium, palladium, iridium, platinum, cobalt, nickel and titanium.
Phosphine complex.
一酸化炭素、これより配位力の弱い単座もしくは二座の
中性配位子、オレフィンまたはジエンを示し、Xは水素
原子、1価の陰イオンまたはトリフェニルホスフィンを
示すか、あるいはXとYが一緒になってβ−ジケトナー
トを示す)で表わされるロジウム−ホスフィン錯体。4. A compound represented by the general formula (2-a) or (2-b): (In the formula, L represents the phosphine compound of claim 1, Y represents carbon monoxide, a monodentate or bidentate neutral ligand having a weaker coordinating force, an olefin or a diene, X represents a hydrogen atom, A rhodium-phosphine complex represented by a monovalent anion or triphenylphosphine, or X and Y together represent β-diketonate).
が、(a)Y=CO、X=ハロゲン原子またはシアノ
基、(b)Y=シクロオクタ−1,5−ジエン、X=ハ
ロゲン原子、ClO4、BF4、PF6、CH3COOまた
はシアノ基、(c)Y=ノルボルナジエン、X=ハロゲ
ン原子、ClO4、BF4、PF6、CH3COOまたはシ
アノ基、(d)Y=(CO)2、X=水素原子または(トリ
フェニルホスフィン)2、(e)Y=(CO)3、Y=トリ
フェニルホスフィン、(f)Y=エチレン、X=ハロゲ
ン原子またはシアノ基、(g)Y=ピリジン、X=塩素
原子または臭素原子、および(h)X,Y=β−ジケト
ナートより選ばれたものである請求項4記載のロジウム
−ホスフィン錯体。5. In the general formula (2), the combination of X and Y is (a) Y = CO, X = halogen atom or cyano group, (b) Y = cycloocta-1,5-diene, X = halogen. Atom, ClO 4 , BF 4 , PF 6 , CH 3 COO or cyano group, (c) Y = norbornadiene, X = halogen atom, ClO 4 , BF 4 , PF 6 , CH 3 COO or cyano group, (d) Y = (CO) 2 , X = hydrogen atom or (triphenylphosphine) 2 , (e) Y = (CO) 3 , Y = triphenylphosphine, (f) Y = ethylene, X = halogen atom or cyano group, ( The rhodium-phosphine complex according to claim 4, wherein g) Y = pyridine, X = chlorine atom or bromine atom, and (h) X, Y = β-diketonate.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP05253893A JP3313805B2 (en) | 1993-03-12 | 1993-03-12 | Phosphine compounds and transition metal-phosphine complexes having the same as ligands |
EP19940103674 EP0614901B1 (en) | 1993-03-12 | 1994-03-10 | Phosphine compound and transition metal-phosphine complex containing the same as ligand |
DE1994612309 DE69412309T2 (en) | 1993-03-12 | 1994-03-10 | Phosphine compound and transition metal-phosphine complex containing this as a ligand |
US08/323,492 US5530150A (en) | 1993-03-12 | 1994-10-12 | Phosphine compound, complex containing the phosphine compound as ligand, process for producing optically active aldehyde using the phosphine compound or the complex, and 4-[(R)-1'-formylethyl]azetidin-2-one derivatives |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP05253893A JP3313805B2 (en) | 1993-03-12 | 1993-03-12 | Phosphine compounds and transition metal-phosphine complexes having the same as ligands |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06263776A true JPH06263776A (en) | 1994-09-20 |
JP3313805B2 JP3313805B2 (en) | 2002-08-12 |
Family
ID=12917556
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP05253893A Expired - Fee Related JP3313805B2 (en) | 1993-03-12 | 1993-03-12 | Phosphine compounds and transition metal-phosphine complexes having the same as ligands |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0614901B1 (en) |
JP (1) | JP3313805B2 (en) |
DE (1) | DE69412309T2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008169201A (en) * | 2006-12-11 | 2008-07-24 | Tokyo Univ Of Agriculture & Technology | Novel optically biaryl phosphorus compound and method for producing the same |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0684230B1 (en) * | 1993-03-12 | 2002-07-03 | Takasago International Corporation | 4- (R)-1'-formylethyl azetidin-2-one derivatives |
DE19516968A1 (en) * | 1995-05-12 | 1996-11-14 | Basf Ag | Optically active phosphines, their production, their metal complexes and their use in asymmetric synthesis |
DE19521340A1 (en) * | 1995-06-12 | 1996-12-19 | Hoechst Ag | Process for the preparation of hydroxybiarylphosphanes and new compounds from this group of substances |
JP3830180B2 (en) * | 1995-07-27 | 2006-10-04 | 高砂香料工業株式会社 | Novel phosphine-phosphinite compound and method for producing 4-[(R) -1'-formylethyl] azetidin-2-one derivative using the same |
JP3892931B2 (en) * | 1997-03-11 | 2007-03-14 | 高砂香料工業株式会社 | Optically active phosphine derivative having two vinyl groups, polymer using the same, and transition metal complexes thereof |
JP3892932B2 (en) * | 1997-03-11 | 2007-03-14 | 高砂香料工業株式会社 | Optically active phosphine derivatives having a vinyl group, polymers using the same, and transition metal complexes thereof |
DE19725796A1 (en) * | 1997-06-18 | 1998-12-24 | Basf Ag | Production of optically active phospholanes, their metal complexes and use in asymmetric synthesis |
DE19725643A1 (en) * | 1997-06-18 | 1998-12-24 | Basf Ag | Optically active diphosphine ligands |
DE19824121A1 (en) | 1998-05-29 | 1999-12-02 | Basf Ag | Production of optically active phospholanes, their metal complexes and use in asymmetric synthesis |
DE19918420A1 (en) * | 1999-04-23 | 2000-10-26 | Aventis Res & Tech Gmbh & Co | New bidentate organophosphorus ligands whose transition metal complexes are useful as catalysts for polymerization and asymmetric synthesis comprise a trivalent phosphine group and another trivalent phosphorus group |
DE10355066A1 (en) | 2003-11-25 | 2005-06-23 | Basf Ag | Process for asymmetric synthesis |
US8097749B2 (en) * | 2008-03-28 | 2012-01-17 | Union Carbide Chemical and Plastics Technology Technology | Isothermal process for phosphoromonochloridite synthesis |
CN112794796B (en) * | 2020-06-30 | 2023-05-12 | 中海油天津化工研究设计院有限公司 | Method for preparing isononyl aldehyde by diisobutylene hydroformylation |
CN111729687B (en) * | 2020-07-08 | 2022-08-05 | 万华化学集团股份有限公司 | Preparation method and application of hydroformylation catalyst |
Family Cites Families (4)
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DK350383A (en) * | 1982-08-27 | 1984-02-28 | Hoffmann La Roche | phosphorus compounds |
JP2733880B2 (en) * | 1991-03-12 | 1998-03-30 | 高砂香料工業株式会社 | Optically active tertiary phosphine compound and transition metal complex containing it as ligand |
US5171892A (en) * | 1991-07-02 | 1992-12-15 | E. I. Du Pont De Nemours And Company | Chiral phospholanes via chiral 1,4-diol cyclic sulfates |
US5360938A (en) * | 1991-08-21 | 1994-11-01 | Union Carbide Chemicals & Plastics Technology Corporation | Asymmetric syntheses |
-
1993
- 1993-03-12 JP JP05253893A patent/JP3313805B2/en not_active Expired - Fee Related
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1994
- 1994-03-10 EP EP19940103674 patent/EP0614901B1/en not_active Expired - Lifetime
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JP2008169201A (en) * | 2006-12-11 | 2008-07-24 | Tokyo Univ Of Agriculture & Technology | Novel optically biaryl phosphorus compound and method for producing the same |
Also Published As
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EP0614901B1 (en) | 1998-08-12 |
DE69412309T2 (en) | 1998-12-17 |
DE69412309D1 (en) | 1998-09-17 |
EP0614901A1 (en) | 1994-09-14 |
JP3313805B2 (en) | 2002-08-12 |
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